Disazo dyestuffs containing a 1, 3-benzo-dioxane group



F 13 Claims. Cl. 260-152) ABSTRACT OF THE DISCLOSURE An azo dyestulf ofthe formula:

\O CH2 wherein R is a residue of the benzene or naphthalene seriesjoined to the two azo groups in p-positions, R is a residue of thebenzene series in which the OH group is in the or p-position to the azobridge, X is a nonionic substituent customarily employed in dyestuifs.

DISCLOSURE The present invention relates to novel azo dyestuifs; moreparticularly it relates to new azo dyestuffs which are free fromsulphonic acid and carboxylic acid groups and which correspond to theformula In this formula R stands for a radical of the benzene ornaphthalene series wherein the azo groups are linked in the p-positionto one another, and R represents a radical of the benzene series inwhich the OH group stands in the 0-position or preferably in thep-position to the azo group; the residues R and R as well as theleft-hand phenylene residue may contain non-ionic substituents customaryin azo dyestuffs, such as halogen, especially fluorine, chlorine and/orbromine, further alkyl groups, particularly lower alkyl groups having 1to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl,isobutyl and amyl, lower alkoxy groups having 1 to 4 carbon atoms, suchas methoxy, ethoxy and propoxy, nitro, cyano, trifiuoromethyl,optionally substituted sulphonamide and carbonamide groups, sulphonicacid lower alkyl ester and carbo lower alkoxy groups having 1 to 3carbon atoms in the alkyl radical; the radicals R and R as well as thelefthand phenylene nucleus may contain 1, 2 or 3 of those non-ionicsubstituents.

In certain embodiments of this invention the novel azo dyestutf has theformula:

wherein R and R have the meanings recited above and X is hydrogen, loweralkyl, lower alkoxy, or halogen, specifically chlorine or bromine. Inpreferred embodi- 3,376,280 Patented Apr. 2, 1968 gen, methyl, ormethoxy, Z is hydrogen, methoxy, hydroxy, or ethoxy, W is hydrogen,methyl, methoxy, or methyl carboxy, and n is the integer 1 or 2.

The new disazo dyestufifs are obtained when a diazotised amino-monoazodyestuff of the formula O OHz 11) wherein R, has the same meaning asabove and wherein the amino group in R stands in the p-position to theazo group, is coupled with a phenol in the o-position or, preferably, inthe p-position to the hydroxyl group, and the starting components areselected so that they are free from sulphonic acid and carboxylic acidgroups.

Coupling of the starting components is preferably carried out in analkaline medium and optionally in the presence of a couplingaccelerator, e.g., formamide, dimethyl formamide or pyridine.

The amino-monoazo dyestuffs (II) are produced in the usual manner bycoupling diazotised :aminobenzodioxans- (1,3) with aminobenzenes oraminonaphthalenes in the p-position to the amino group.

Suitable diazo components for the synthesis of the amino-monoazodyestuflfs (II) are, for example, 6-aminobenzodioxan-(1,3),6-amino-7-methyl-benzodioxan-( 1,3 6 amino 8 methyl benzodioxan- (1,3),6-amino-7-methoxy benzodioxan 1,3 6-amino-7-chloroor-bromobenzodioxan(1,3) and 6 amino-8-chloro-benzodioxan- (1,3). The aforesaidaminobenzodioxans can be produced, for example, according to W. Borscheand A. D. Berkhout (Annalen der Chemie 330 [1904], page 82), bycondensing 4-nitro-1-hydroxybenzene or its nuclearsubstitutedderivatives with 2 mol formaldehyde and reducing the resultant6-nitrobenzodioxans-(1,3) to the 6- amino compounds. Suitable couplingcomponents R -NH are, inter alia, aniline, 1-amino-3-methylbenzene,l-amino 3,5- and 3,6 dimethylbenzene, 1 amino 2-methoxy-5-methylbenzene, 1-amino-3-methoxybenzene, 1-amino-3, 6 dimethoxybenzene,1 amino 3,6-diethoxybenzene, 1- amino naphthalene, 1 amino2-ethoxynaphthalene, 1- amino 5 hydroxy-naphthalene,l-amin0-5,6,7,8-tetrahydronaphthalene.

The following phenols and phenol derivatives can be used for couplingwith the diazo compounds of the aminomonoazo components (II), forexample: phenol, l hydroxy 2 methylbenzene, 1 hydroxy 3 methylbenzene, 1hydroxy benzene 2 carboxylic acid methyl ester, 1 hydroxy benzene 2carboxylic acid ethyl ester, 1 hydroxy 2 methoxybenzene, 1 hydroxy 4-methylbenzene, 1 hydroxy 3 methoxybenzene, '1 hydroxy 3 chlorobenzene, 1hydroxy 3,5- and -3,6- dimethylbenzene, 1 hydroxy 3 methyl 5ethylbenzene and 1 hydroxy 3 methyl 5 isopropylbenzene.

The new dyestuflls (I) are valuable products which are especiallysuitable for the dyeing and printing of fibres and fabrics ofhydrophobic materials, preferably of aroand dyes materials ofpolyethylene terephthalate fibres matic polyesters, such as polyethyleneterephthalates and and polyesters from terephthalic acid and 1,4 bishypolyesters from terephthalic acid and 1,4 bis hydroxydroxymethylcyclohexane, and materials of polyamides methyl cyclohexane, andmaterials of 2 /2- and triand 2 /zand triacetyl cellulose in stronglyyellowish acetate. Yellow, orange and red to brown shades are 5 orangeshades with good fastness properties. obtained which are distinguishedby good fastness properties, such as fastness to light and sublimation,ironing EXAMPLE 2 and wet processing. The dyestuffs are also eminentlysuitable for the dyeing and printing of synthetic super- P y Weight ofthfi amino mofloalo y f Poly-amide and polyurethane fib The novel d t ffobtainable 1n the usual manner from drazotised ammo are furtherdistinguished by their excellent drawing power benzo dlOXan 1 amlnOdlmetbOXY- on fibrous mat i l f a i polyesters benzenes, are suspendedin 600 parts by volume of water, The following examples are given forthe purpose of followed the addlflofl P 28 P y Volume of illustratingthe invention. n r dhydrochlonc ac1d.

Diazotrsation is then carried out in the usual manner EXAMPLE 1 with 24parts by volume of a 30% aqueous sodium nitrite 26.9 parts b Weight ofth amino monoazo dyestufi' solution. The diazotised monoazo dyestulfslowly disobtainable in the usual manner from diazotised 6 aminosolves.This aqueous solution is clarified and added to benzo dioxan (1,3) and lamino 3 rnethylbenzene, a soda alkaline solution of 9,4 parts by weightof hyare suspended in 600 parts by volume of water, followeddroxybenzene in 180 parts by volume of water, w'here-. by the additionof 28 parts by volume of concentrated upon a precipitate separates.After completion of the hydrochloric acid. Diazotisation is then carriedout in the coupling, the resultant disazo dyestuff is filtered off withusual manner with 24 parts by volume of a 30% aquesuction and washed.The dyestulf obtained dyes materials ous sodium nitrite solution. Thediazotised monoazo dyef polyethylene terephthalate fibres and polyestersfrom stud slowly dissolves. This aqueous solution is clarified 25terephthalic acid and 1,4 bis hydroxy methyl 1 and added to aSoda-alkaline Solution of Parts by hexane, and materials of polyarnideand acetylated cel- Waight 0f hydroxybenzene in 180 Parts by Volume oflulose in reddish orange shades with good fastness propwater, whereupona precipitate separates. After compleerties tion of the coupling, theresultant disazo dyestufi 1s -fi1- By using equivalent amounts of thestarting compo tered OE With Suction and Washed The dyestufi Obtainednents given in the following table and proceeding othercorresponds tothe formula wise in analogy with the instructions of Example 1 or 2,;

O N=N valuable disazo dyestutfs are also obtained, which dye polyester,polyamide and acetate fibres in the stated shades.

Diazo component 1st Coupling component 2nd Coupling component Shade1-hydroxy-3-methylbenzene Strongly yellowish orange.

l-amino-l-l-methylbenzene 1-hydroxy-2-methylbenzeue Strongly reddishyellow.

l-hydroxybenzene-2-earboxylie acid Yellowish orange. methyl ester. Do d0l-hydroxy--methylbenzene Rcddish yellow.6-amino7-n1ethyl-benzo-dioxan-(l,3) 1-amino-2-n1ethoxy-5-methylbenzenel-hgldrloxybenzene-earhoxylic acid Orange.

e y ester.

6-aminobenzodioxan-(1,3) 1-amino-3,5-dimethyl-henzene l-hydroxy-benzeneYellowish orange. 1-hydroxy-2-methylbenzene. Do. 1-hydroxy-3-methylbenzene Do. Hydroxybenzene Do.

6-amino-8 6-amino-7-chloro-benzo-dioxan-(1,3) ..d 0 DG-aminobenzodioxan-(l 3) l-amlno-li-methoxybenzenc.. .do... Reddishyellow.

Do ydroxy-Z-methylbenzene. Do.

Do... l-hydroxy-3-methylbenzene. Strongly yellowish orange.

Do l-hydroxy-lfrdimethyl-benzene. Do.

Do l-hydroxybenzenc-2-earboxy1ic acid Do.

ethyl ester.

Do 1-hydroxy-3,5-dimethylbenzene Orange.

Do 1-11ydroxy-S-methoxybenzene Do.

Do ..do Yellowish orange.

Dom. d 1-hydroxy-3, dimethylbenzene. Do.

Do ..d0. 1,3-dihydroxybenzene Yellow-brown.

D 1-amin0-2,5-dimethylbenzene 1-hydroxy-3-methylbenzene. Orange.

Do 1-amino-2-methoxy-5-rnethylbenzene. Hydroxybenzene Yellowish orange.

Do. l-hydroxy-2-methylbenzene. Orange.

Do d l-hydroxy-B-methylbenzene. Do.

Do .d0 Rcddish orange.

Do d 1-hydroxy-3-methoxybenzene. Red.

Do Hydroxybenzene Orange.

Do. d 1-hydroxy3-methylb Reddish orange.

Do. 1-hydroxy-3,fi-dimethylbeuz Do.

Do, do. l-hydroxy-Zi-methoxybenzene Strongly reddish orange.

D l-amino-Z-methoxynaphthalene Hydroxybenzene Red.

D0, l-amino-zsdimethoxybenzene. 1-hydroxy-2,fi-dimethylbenzen Orange.

Do. l-hydroxy-B-methoxybenzene. Red.

Laminonaphthalene...

D l-hydroxy-Zanethylbenzenev Orange. D l-amino-3-methylbenzene.1-hydroxy2,5dimethylbenzene. Yellowish orange. DLamino-2,5-diu1ethylbenzene Hydroxybenzene Do. l-hydroxy-2-methylbenzeneDo. 1-hydroxy-3,5-dirnethylbenzene. Do. l-hydroxy-2,5-dimethylbenzeneReddish yellow. 1-hydroxy-3-methoxybenzene Orange.l-hydr0xybenzene-2-carboxylic acid Reddish yellow.

methylester. 1,3-dihydroxybenzene Orange.

l-hydroxy-2,5-dimethylbenzenc l-hydroxy-Il,5-dirnethylbenzene.

1-hydroxy-34nethoxybenzene. 1,3dihydroxyb'enzene Red.l-hydroxybenzene-2'earb0xylic acid Yellowish orange.

methylester.

. Yellowish orange.

. Scarlet.

5 We claim: 1. An azo dyestuff of the formula /O- N=NR1N=NR2OH H2C IOCHz wherein R stands for a residue selected from the class consistingof residues of the benzene and naphthalene series and joined to the twoazo groups in p-positions, R stands for a residue of the benzene seriesin which the OH group is in the or p-position to the azo bridge, Xstands for a member selected from the class consisting of hydrogen,lower alkyl, lower alkoxy, chlorine and bromine; the dyestutf being freeof sulfonic and carboxylic acid groups.

2. A dyestuff of the formula wherein Y stands for a member selected fromthe class consisting of -H, CH and Cl, Z stands for a member selectedfrom the class consisting of H, OCH -OH, and OC H W stands for a memberselected from the class consisting of H, -CH -OCH and COOCH and n standsfor an integer ranging from 1 to 2.

3. A dyestuif of the formula wherein Y stands for a member selected fromthe class consisting of -H, CH and Cl, Z stands for a member selectedfrom the class consisting of H, -CH

and -OCH n stands for an integer ranging from 1 to 2, and W stands for amember selected from the class consisting of H, -CH OCH and COOCH 4. Thedyestuff of the formula 5. The dyestuff of the formula I 0CHz CH3 6. Thedyestuff of the formula O-CHI 0 0 H3 7. The dyestuff of the formula H20I I 9. The dyestuff of the formula 11. The dyestufi of the formula OCHaCH; 12. The dyestulf of the formula 0 O CH; $113 H2O I I I OCHQ CH3 CH;13. The dyestulf of the formula I OH;

References Cited UNITED STATES PATENTS 2,391,137 12/1945 Danuser et al.260-152 2,468,277 4/1949 Strouse 260-452 FLOYD D. HIGEL, PrimaryExaminer.

